Anodeless lithium metal battery and method of manufacturing the same

ABSTRACT

An anodeless lithium metal battery includes: a cathode including a cathode current collector and a cathode active material layer on the cathode current collector; an anode current collector on the cathode; and a composite electrolyte between the cathode and the anode current collector, wherein the composite electrolyte includes a first liquid electrolyte and at least one of lithium metal or a lithium metal alloy.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean PatentApplication No. 10-2018-0001850, filed on Jan. 5, 2018, in the KoreanIntellectual Property Office, and all the benefits accruing therefromunder 35 U.S.C. § 119, the content of which is incorporated herein byreference in its entirety.

BACKGROUND 1. Field

The present disclosure relates to an anodeless lithium metal battery anda method of manufacturing the same.

2. Description of the Related Art

A lithium secondary battery is a high-performance battery having thehighest energy density as compared to other currently availablesecondary batteries, and are applicable to various fields such aselectric vehicles.

A lithium secondary battery may use a lithium metal thin film as ananode. A lithium metal thin film may be formed by roll-pressing lithiuminto a planar form. However, a lithium secondary battery using a lithiummetal thin film as the anode may have insufficient energy density andlifetime characteristics due to the formation and growth of dendrites onthe lithium metal thin film. Therefore, there is a need for an improvedanode material.

SUMMARY

Provided is an anodeless lithium metal battery having improved energydensity.

Provided is a method of manufacturing the anodeless lithium metalbattery.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description, or may belearned by practice of the presented embodiments.

According to an aspect of an embodiment, an anodeless lithium metalbattery includes: a cathode including a cathode current collector and acathode active material layer on the cathode current collector; an anodecurrent collector on the cathode; and a composite electrolyte betweenthe cathode and the anode current collector, wherein the compositeelectrolyte includes a first liquid electrolyte and a metal including atleast one of lithium metal or a lithium metal alloy.

According to an aspect of another embodiment, a method of manufacturingthe anodeless lithium metal battery includes: combining a metalincluding at least one of lithium metal or a lithium metal alloy withthe first liquid electrolyte to prepare a composite electrolytecomposition; coating the composite electrolyte composition on the anodecurrent collector; drying the coated composite electrolyte compositionto prepare the composite electrolyte; and disposing the anode currentcollector and the composite electrolyte on the cathode including thecathode active material layer on a cathode current collector tomanufacture the anodeless lithium metal battery.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects will become apparent and more readilyappreciated from the following description of the embodiments, taken inconjunction with the accompanying drawings in which:

FIG. 1A is a schematic view illustrating a structure of an embodiment ofan anodeless lithium metal battery;

FIG. 1B illustrates structure of an embodiment of a compositeelectrolyte and an embodiment of a solid electrolyte in the anodelesslithium metal battery of FIG. 1A;

FIG. 1C illustrates a detailed structure of an embodiment of a lithiummetal particle in the composite electrolyte, and illustrates anexpansion mechanism of the lithium metal particle in the compositeelectrolyte;

FIG. 2A is a graph of capacity (milliampere-hours, mAh) versus number ofcycles (n) in an anodeless lithium metal battery manufactured in Example1;

FIG. 2B is a graph of coulombic efficiency (percent, %) versus number ofcycles (n), in an anodeless lithium metal battery manufactured inaccordance with Example 1;

FIG. 3A is a graph of capacity (mAh) versus number of cycles (n) in ananodeless lithium metal battery manufactured in Comparative Example 1;

FIG. 3B is a graph of coulombic efficiency (%) versus number of cycles(n) in an anodeless lithium metal battery manufactured in accordancewith Comparative Example 1;

FIG. 4A is a graph of capacity (mAh) versus number of cycles (n) in alithium metal battery manufactured in Comparative Example 2;

FIG. 4B is a graph of coulombic efficiency (%) versus number of cycles(n) in an anodeless lithium metal battery manufactured in accordancewith Comparative Example 2;

FIG. 5 is a graph of capacity (mAh) versus number of cycles (n) showingrate capability of the lithium metal batteries of Example 1 andComparative Example 2;

FIG. 6A is a graph of imaginary impedance (−Z, ohm) versus realimpedance (Z′, ohm), illustrating initial impedance characteristics ofthe anodeless lithium metal batteries of Example 1 and ComparativeExample 1; and

FIG. 6B is a graph of imaginary impedance (−Z, ohm) versus realimpedance (Z′, ohm), illustrating impedance characteristics after onecycle in the anodeless lithium metal batteries of Example 1 andComparative Example 1.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments, examples of whichare illustrated in the accompanying drawings, wherein like referencenumerals refer to like elements throughout. In this regard, the presentembodiments may have different forms and should not be construed asbeing limited to the descriptions set forth herein. Accordingly, theembodiments are merely described below, by referring to the figures, toexplain aspects.

It will be understood that when an element is referred to as being “on”another element, it can be directly on the other element or interveningelements may be present therebetween. In contrast, when an element isreferred to as being “directly on” another element, there are nointervening elements present.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms, including “at least one,” unless the content clearly indicatesotherwise. “At least one” is not to be construed as limiting “a” or“an.” As used herein, the term “and/or” includes any and allcombinations of one or more of the associated listed items. Expressionssuch as “at least one of,” when preceding a list of elements, modify theentire list of elements and do not modify the individual elements of thelist.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items. It will be furtherunderstood that the terms “comprises” and/or “comprising,” or “includes”and/or “including” when used in this specification, specify the presenceof stated features, regions, integers, steps, operations, elements,and/or components, but do not preclude the presence or addition of oneor more other features, regions, integers, steps, operations, elements,components, and/or groups thereof.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±20%, 10% or 5% of the stated value.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this disclosure belongs. It willbe further understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art and thepresent disclosure, and will not be interpreted in an idealized oroverly formal sense unless expressly so defined herein.

Hereinafter, an embodiment of an anodeless lithium metal battery and amethod of manufacturing the anodeless lithium metal battery will bedescribed in greater detail.

In accordance with an aspect of the disclosure, an anodeless lithiummetal battery includes: a cathode current collector; a cathode includinga cathode active material layer; an anode current collector; and acomposite electrolyte including a first liquid electrolyte and at leastone of lithium metal or a lithium metal alloy.

In a lithium metal battery using a lithium metal thin film as an anode,a dead volume of lithium may be generated in the battery due to alithium dendrite on the lithium metal thin film. While not wanting to bebound by theory, it is understood that the dendrite forms and growsafter during charge and discharge. The formation of the lithium dendriteis understood to lead to a loss of electrochemically active lithium, andconsequently reducing the lifetime and capacity characteristics of thelithium metal battery. In addition, because the lithium metal thin filmis planar in form, the lithium metal thin film may swell only in anupper or lower portion of the electrode during charge. As a result, itmay be difficult to control the volume expansion of the lithium metalbattery during charge and discharge within a desired range.

To solve this problem, the inventors have advantageously discovered thatuse of an anode current collector without a planar lithium metal thinfilm, together with a composite electrolyte comprising at least one oflithium metal or a lithium metal alloy, and a liquid electrolyte,results in improved energy density and charge-discharge efficiency of alithium metal battery. While not wanting to be bound by theory, it isunderstood that in the anodeless lithium metal battery according to anembodiment, an individual metal particle of the lithium metal or lithiummetal alloy in the composite electrolyte may freely expand, so that theabove-described drawbacks associated with the lithium metal batteryincluding a lithium metal thin film are avoided.

As used herein, the term “anodeless lithium metal battery” refers to alithium metal battery which does not include an anode active material onthe anode current collector before the first charge. In further detail,the disclosed anodeless lithium metal battery: i) does not include ananode active material, such as graphite, that would intercalate anddeintercalate lithium ions, ii) has, on an anode current collector whenthe battery is assembled or after a first charge, a lithium metal thinfilm or a lithium alloy thin film as an anode having a thickness ofabout 10% or less with respect to a thickness of a cathode, and iii)does not include an anode active material layer when the battery isassembled and before the first charge. The expression “thickness of theanode” may refer to a total thickness of the anode current collector andthe anode active material layer. Thus while the anodeless lithium metalbattery has a negative electrode, the term “anodeless” is used becausewhen manufactured a distinct anode active material is not present.

An anodeless lithium metal battery according to an embodiment will befurther described with reference to FIGS. 1A and 1B. FIG. 1A is aschematic view illustrating a structure of an anodeless lithium metalbattery and FIG. 1B is an illustration showing the structures of a solidelectrolyte 13, a composite electrolyte 12, and an anode currentcollector 11 in the anodeless lithium metal battery of FIG. 1A.

Referring to FIG. 1A, the anodeless lithium metal battery according toan embodiment may include the composite electrolyte 12 on the anodecurrent collector 11. As noted above, a planar lithium metal thin filmis not used in the manufacture of the anodeless lithium metal battery.The composite electrolyte 12 comprises a metal, e.g., a metal particle12 a, which comprises at least one of lithium metal or a lithium metalalloy, which is distributed or dispersed in a first liquid electrolyte12 b.

The composite electrolyte 12 may further include a non-woven fabric 12c, as illustrated in FIG. 1B. The non-woven fabric 12 c may support themetal particle 12 a of a lithium metal and/or a lithium metal alloy. Thenon-woven fabric 12 c may be omitted. For example, when the anodecurrent collector 11 is a mesh-type, the non-woven fabric 12 c may notbe present.

The first liquid electrolyte 12 b may be uniformly distributed in thecomposite electrolyte 12. The first liquid electrolyte 12 b may includea lithium salt and an organic solvent. A concentration of the lithiumsalt may be about 1 molar (M) to about 8 M, and in some embodiments,about 2 M to about 5 M, and in some other embodiments, about 2 M toabout 4 M.

The first liquid electrolyte 12 b may be, for example, ahigh-concentration electrolyte solution, for example, a solutionincluding a high-concentration of the lithium salt. For example, thehigh-concentration electrolyte solution may be an electrolyte solutioncontaining a lithium salt in a concentration of about 1 M to about 8 M,and in some embodiments, about 2 M to about 5 M, and in some otherembodiments, about 2 M to 4 M.

Referring to FIG. 1A, a cathode 18 may include a cathode currentcollector 14 and a cathode active material layer 15 disposed on thecathode current collector 14. The cathode active material layer 15 mayinclude a cathode active material and a second liquid electrolyte. Asolid electrolyte 13 may be disposed between the cathode 18 and thecomposite electrolyte 12 such that the cathode 18 and the compositeelectrolyte 12 are separated from one another.

The solid electrolyte 13 may block the second liquid electrolyte in thecathode 18 from migrating toward the composite electrolyte 12, or thefirst liquid electrolyte in the composite electrolyte 12 from migratingtoward the cathode 18.

A porous polymer membrane 16 may be disposed between the solidelectrolyte 13 and the composite electrolyte 12 such that direct contactbetween the solid electrolyte 13 and the composite electrolyte 12 isprevented. The porous membrane 16, though illustrated in both of FIGS.1A and 1B, may be omitted. Referring to FIG. 1A, a barrier 17 forprotecting the solid electrolyte 13 may be included. The barrier 17 mayhave any suitable structure, not limited to the structure of FIG. 1A,provided that it sufficiently protects the solid electrolyte 13. Thebarrier 17 may comprise, for example, a material of a battery case,e.g., a metallized film as used for a case of a pouch cell.

The solid electrolyte 13 may separate the composite electrolyte 12 fromthe cathode 18. Because the solid electrolyte 13 separates the compositeelectrolyte 12 from the cathode 18, the anodeless lithium metal batteryaccording to an embodiment may be manufactured as a separate cell typebattery. The separate cells may be used as dual chamber cells. The solidelectrolyte 13 may allow only lithium ions to pass through, and blocksthe passage or permeation of liquid, for example.

The solid electrolyte 13 may be an inorganic solid electrolyte, anorganic solid electrolyte, or an organic/inorganic compositeelectrolyte. The organic solid electrolyte may include, for example, atleast one of a polyethylene derivative, a polyethylene oxide derivative,a polypropylene oxide derivative, a phosphoric acid ester polymer,polyester sulfide, polyvinyl alcohol, or polyvinylidene fluoride. Theinorganic solid electrolyte may include, for example, at least one of aglassy active metal ionic conductor, an amorphous active metal ionicconductor, a ceramic active metal ionic conductor, or a glass-ceramicactive metal ionic conductor. The organic/inorganic compositeelectrolyte may be, for example, a combination of an organic solidelectrolyte and an inorganic solid electrolyte as listed above.

The solid electrolyte 13 may comprise at least one ofLi_(1+x)Ti_(2−x)Al(PO₄)₃ (LTAP) (wherein 0≤x≤4), a Li—Ge—P—S-basedmaterial, Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ (wherein 0<x<2 and0≤y<3), BaTiO₃, Pb(Zr_(1−x)Ti_(x))O₃ wherein 0≤x≤1 (PZT),Pb_(1−x)La_(x)Zr_(1−y)Ti_(y)O₃ (PLZT) (wherein 0≤x<1 and 0≤y<1),Pb(Mg_(1/3)Nb_(2/3))O₃—PbTiO₃ (PMN-PT), HfO₂, SrTiO₃, SnO₂, CeO₂, Na₂O,MgO, NiO, CaO, BaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, TiO₂, SiO₂, SiC, lithiumphosphate (Li₃PO₄), lithium titanium phosphate (Li_(x)Ti_(y)(PO₄)₃,wherein 0<x<2, and 0<y<3), lithium aluminum titanium phosphate(Li_(x)Al_(y)Ti_(z)(PO₄)₃, wherein 0≤x≤2, 0≤y≤1, and 0≤z≤3),Li_(1+x+y)(Al_(1−a)Ga_(a))_(x)(Ti_(1−b)Ge_(b))_(2−x)Si_(y)P_(3−y)O₁₂(wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, 0≤b≤1), lithium lanthanum titanate(Li_(x)La_(y)TiO₃, wherein 0<x<2 and 0<y<3), lithium germaniumthiophosphate (Li_(x)Ge_(y)P_(z)S_(w), wherein 0<x<4, 0<y<1, 0<z<1, and0<w<5), lithium nitride (Li_(x)N_(y), wherein 0<x<4 and 0<y<2), a SiS₂(Li_(x)Si_(y)S_(z), wherein 0<x<3, 0<y<2, and 0<z<4) glass, a P₂S₅ glass(Li_(x)P_(y)S_(z), wherein 0<x<3, 0<y<3, and 0<z<7), Li₂O, LiF, LiOH,Li₂CO₃, LiAlO₂, a Li₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂ ceramic,LixAl_(y)Ti_(z)(PO₄)₃, wherein 0<x<2, 0<y<1, and 0<z<3, or a garnetceramic such as Li_(3+x)La₃M₂O₁₂, wherein 0≤x≤5 and M is Te, Nb, or Zr.

The solid electrolyte 13 may comprise at least one ofLi_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂, Li_(1.3)Ti_(1.7)Al_(0.3)P₃O₁₂,Li₁₀GeP₂S₁₂, Li₇La₃Zr₂O₁₂ (LLZ), lithium phosphorous oxynitride (LiPON),Li₅La₃Ta₂O₁₂, Li_(0.33)La_(0.55)TiO₃, Li_(1.5)Al_(0.5)Ge_(1.5)P₃O₁₂,Li₃BO₃, Li₄SiO₄—Li₃PO₄, Li₄SiO₄, Li_(1/3)La_(1/3)TiO₃, orLi₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂.

The solid electrolyte 13 may be in the form of a membrane, and may havea thickness of about 10 micrometers (μm) to about 150 μm, and in someembodiments, about 15 μm to about 90 μm, and in some other embodiments,about 20 μm to about 50 μm.

The non-woven fabric 12 c, as shown in FIG. 1B, may have a porosity ofabout 10% to about 90%, and in some embodiments, about 10% to about 80%,and in some other embodiments, about 10% to about 50%, and in some otherembodiments, about 25% to about 50%, based on a total volume of thenon-woven fabric, and may have an average pore size of about 0.1 μm toabout 10 μm, and in some embodiments, about 0.1 μm to about 8 μm, and insome other embodiments, about 0.1 μm to about 1.0 μm. As used herein,the term “average pore size” may refer to an average diameter of a porewhen the pores are spherical in shape, or may refer to a length of thelonger axis of a pore when the pores are non-spherical. The pore sizemay be determined by microscopy, for example.

The non-woven fabric 12 c may comprise at least one of cellulose, apolyester (for example, polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), or polyethylene naphthalate (PEN)), polyetherimide,polyethylene, polypropylene, polyamide (e.g., nylon), polyacetal,polycarbonate, polyimide, polyether ketone, polyether sulfone,polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene,polyvinylidene fluoride, polyvinyl chloride, polyacrylonitrile, orpolypara-phenylene benzobisoxazole.

The porous polymer membrane 16 may have a thickness of about 5 μm toabout 30 μm, and in some embodiments, about 10 μm to about 20 μm orabout 10 μm to about 15 μm. The porous polymer membrane 16 may compriseat least one of a polyethylene membrane, a polypropylene membrane, apolyester membrane such as a polyethylene terephthalate membrane, apolybutylene terephthalate membrane, or a polyethylene naphthalatemembrane, a polyacetal membrane, a polyamide membrane, a polycarbonatemembrane, a polyimide membrane, a polyether ketone membrane, a polyethersulfone membrane, a polyphenylene oxide membrane, or a polyphenylenesulfide membrane.

FIG. 1C is an illustration of a detailed structure of a metal particle12 a in the composite electrolyte 12 according to an embodiment, forexplaining an expansion mechanism of the metal particle in the compositeelectrolyte. Referring to FIG. 1C, in the anodeless lithium metalbattery according to an embodiment, the metal particle 12 a of at leastone of lithium metal or a lithium metal alloy in the compositeelectrolyte 12 including the first liquid electrolyte 12 b, may bepresent in the form of an independent metal particle and thus may freelyexpand in a radial direction, thereby preventing the loss of lithiumduring charge and discharge.

In a lithium metal battery including a lithium metal thin film,deposition of lithium ions occurs on the lithium metal thin film duringcharge. However, and without being limited by theory, it is believedthat in the disclosed lithium metal battery the composite electrolyte 12may release a lithium ion during discharge, and the lithium ion maymigrate to the at least one of lithium metal or a lithium metal alloy inthe composite electrolyte 12 during charge, and then be electrodepositedon a surface of the at least one of lithium metal and a lithium metalalloy. Through these processes the at least one of lithium metal or alithium metal alloy may form an interconnected structure, and thisinterconnected structure may be bound to and/or disposed on a surface ofthe anode current collector 11.

In an embodiment, the first liquid electrolyte of the compositeelectrolyte and the second liquid electrolyte of the cathode may bedifferent from one another. When the compositions of the first liquidelectrolyte and the second liquid electrolyte are different from eachother, the compositions of the first and second liquid electrolytes maybe independently selected, e.g., to compensate for any electrochemicaldisadvantages of the anodeless lithium metal battery, such ashigh-voltage oxidation and electrolyte loss due to dendrite growth.

The first liquid electrolyte and the second liquid electrolyte may eachindependently include at least one of an ionic liquid and a polymerionic liquid (PIL).

The ionic liquid may be an ionic material in a molten (i.e., liquid)state at room temperature (25° C.), and which includes a cation and ananion. For example, the ionic liquid may include a cation comprising atleast one of an imidazolium cation, an ammonium cation, a pyrrolidiniumcation, or a piperidinium cation. However, embodiments are not limitedthereto. For example, the ionic liquid may include an anion comprisingat least one of bis(fluorosulfonyl)imide, fluorosufonylamide,fluoroborate, or a fluorophosphate. However, embodiments are not limitedthereto. Non-limiting examples of the cation include an alkyl ammoniumsuch as triethyl ammonium, an imidazolium such as ethyl methylimidazolium or butyl methyl imidazolium, a pyrrolidium such as1-methyl-1-propylpyrrolidium, or methyl propylpiperidium. A combinationcomprising at least one of the foregoing cations may be used.Non-limiting examples of the anion includebis(trifluoromethylsulfonyl)imide (TFSI),bis(pentafluoroethylsufonyl)imide (BETI), tetrafluoroborate (BF₄), andorthohexafluorophosphate (PF₆). A combination comprising at least one ofthe foregoing anions may be used.

The ionic liquid may be, for example, [emim]Cl/AlCl₃ (wherein emim isethyl methyl imidazolium), [bmpyr]NTf₂ (wherein bmpyr is butyl methylpyridinium and NTf₂=bis(trifluoromethanesulfonyl)imide), [bpy]Br/AlCl₃(wherein bpy is 4,4′-bipyridine), [choline]Cl/CrCl₃.6H₂O,[emim]OTf/[hmim]I (wherein hmim is hexyl methyl imidazolium),[choline]Cl/HOCH₂CH₂OH, [Et₂MeN(CH₂CH₂OMe)]BF₄ (wherein Et is ethyl, Meis methyl, Pr is propyl, Bu is butyl, Ph is phenyl, Oct is octyl, andHex is hexyl), [Bu₃PCH₂CH₂C₈F₁₇]OTf (wherein OTf is trifluoromethanesulfonate), [bmim]PF₆ (wherein bmim is butyl methyl imidazolium),[bmim]BF₄, [omim]PF₆ (wherein omim is octyl methyl imidazolium),[Oct₃PC₁₈H₃₇]I, [NC(CH₂)₃mim]NTf₂ (wherein mim is methyl imidazolium),[Pr₄N][B(CN)₄], [bmim]NTf₂, [bmim]Cl, [bmim][Me(OCH₂CH₂)₂OSO₃],[PhCH₂mim]OTf, [Me₃NCH(Me)CH(OH)Ph] NTf₂, [pmim][(HO)₂PO₂] (wherein pmimis propyl methyl imidazolium), [(6-Me)bquin]NTf₂ (wherein bquin is butylquinolinium, [bmim][Cu₂Cl₃], [C₁₈H₃₇OCH₂mim]BF₄ (wherein mim is methylimidazolium), [heim]PF₆ (wherein heim is hexyl ethyl imidazolium),[mim(CH₂CH₂O)₂CH₂CH₂mim][NTf₂]₂ (wherein mim is methyl imidazolium),[obim]PF₆ (wherein obim is octyl butyl imidazolium), [oquin]NTf₂(wherein oquin is octyl quinolinium), [hmim][PF₃(C₂F₅)₃], [C₁₄H₂₉mim]Br(wherein mim is methyl imidazolium), [Me₂N(C₁₂H₂₅)₂]NO₃, [emim]BF₄,[MeN(CH₂CH₂OH)₃], [MeOSO₃], [Hex₃PC₁₄H₂₉]NTf₂, [emim][EtOSO₃],[choline][ibuprofenate], [emim]NTf₂, [emim][(EtO)₂PO₂], [emim]Cl/CrCl₂,or [Hex₃PC₁₄H₂₉]N(CN)₂. However, embodiments are not limited thereto.Any suitable material that may be used as the ionic liquid in the artmay be used.

Unless specified otherwise, emim is ethyl methyl imidazolium, bmpyr isbutyl methyl pyridinium, bpy is 4,4′-bipyridine, hmim is hexyl methylimidazolium, Et is ethyl, Me is methyl, Pr is propyl, Bu is butyl, Ph isphenyl, Oct is octyl, Hex is hexyl, obim is octyl butyl imidazolium,bmim is butyl methyl imidazolium, omim is octyl methyl imidazolium, mimis methyl imidazolium, pmim is propyl methyl imidazolium, bquin is butylquinolinium, mim is methyl imidazolium, heim is hexyl ethylimidazolium), and oquin is octyl quinolinium.

The polymer ionic liquid may be a polymeric ionic compound consisting ofan organic cation including an imidazolium group, and at least one of anorganic or inorganic anion. The cation of the polymer ionic liquid mayinclude at least one of poly(1-vinyl-3-alkylimidazolium),poly(1-allyl-3-alkylimidazolium), orpoly(1-(meth)acryloyloxy-3-alkylimidazolium), each wherein the alkylgroup may have 1 to 6 carbon atoms. The anion of the polymer ionicliquid may include at least one of CH₃COO⁻, CF₃COO⁻, CH₃SO₃ ⁻, CF₃SO₃ ⁻,(CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻, (CF₃CF₂SO₂)₂N⁻, C₄F₉SO₃ ⁻, C₃F₇COO⁻, or(CF₃SO₂)(CF₃CO)N⁻.

The polymer ionic liquid may be, for example, at least one ofpoly(l-vinyl-3-alkylimidazolium), poly(l-allyl-3-alkylimidazolium), orpoly(1-(meth)acryloyloxy-3-alkylimidazolium), each wherein the alkylgroup may have 1 to 6 carbon atoms. The anion of the polymer ionicliquid may include at least one of CH₃COO⁻, CF₃COO⁻, CH₃SO₃ ⁻, CF₃SO₃ ⁻,(CF₃SO₂)₂N⁻, (CF₃SO₂)₃C⁻, (CF₃CF₂SO₂)₂N⁻, C₄F₉SO₃ ⁻, C₃F₇COO⁻, or(CF₃SO₂)(CF₃CO)N⁻.

The metal particle of lithium metal or a lithium metal alloy may have asize of about 5 micrometers (μm) to about 50 μm, and in someembodiments, about 10 μm to about 50 μm, or about 10 μm to about 30 μm.As used herein, the term “size” may refer to an average particlediameter when the metal particle is in the form of a spherical particle,or may refer to a length of the longest axis when the metal particle isin the form of non-spherical particles.

The metal particle may be at least one of a lithium metal powder or alithium metal alloy powder.

The size of the particle may be measured by laser diffraction particlesize distribution analysis (i.e., laser diffraction scattering). In anembodiment the metal particle may have a coating on the lithium metal orlithium metal alloy.

The metal particle may be treated so as to have a coating layer that isstable in air on a core of the lithium metal or lithium metal alloyparticle. When the particle comprises a coating layer, the averageparticle diameter of the metal particle refers to the size of thelithium metal and/or lithium metal alloy core without the coating layer.The coating layer may be formed by coating the metal particle with, forexample, a coating material including an organic rubber such as nitrilebutadiene rubber (NBR) or styrene butadiene rubber (SBR), an organicresin such as an ethylene vinyl alcohol (EVA) copolymer resin, or aninorganic compound, for example, a metal carbonate such as Li₂CO₃ or ametal oxide such as Li₂O. A combination comprising at least one of theforegoing coating materials may be used. When the metal particle hassuch a coating layer, it may be possible to prevent highly reactivelithium (Li) from reacting with moisture present in the air or a solventand/or moisture present in a dispersion medium.

The lithium metal alloy may include lithium (Li), and at least one ofSi, Sn, Al, Ge, Pb, Bi, Sb, Mg, In, Ca, Ti, V, a Si—Y′ alloy (wherein Y′may be at least one of an alkaline metal, an alkaline earth metal, aGroup 13 to Group 16 element, a transition metal, or a rare earthelement, but is not Si), a Sn—Y′ alloy (wherein Y′ may be at least oneof an alkaline metal, an alkaline earth metal, a Group 13 to Group 16element, a transition metal, or a rare earth element, but is not Sn), orMnO_(x) (wherein 0<x≤2). For example, the lithium metal alloy may be alithium-aluminum (Li—Al) alloy, a lithium-magnesium alloy, a lithium-tinalloy, a lithium-indium alloy, a lithium-calcium alloy, alithium-titanium alloy, or a lithium-vanadium alloy.

A content of the metal particle may be about 1 part by weight to about50 parts by weight, and in some embodiments, about 5 parts by weight toabout 40 parts by weight, and in some other embodiments, about 15 partsby weight to about 30 parts by weight, with respect to 100 parts byweight of a total weight of the composite electrolyte. When the amountof the metal particle is within these ranges, the anodeless lithiummetal battery may have improved initial efficiency and capacitycharacteristics. In the anodeless lithium metal battery according to oneor more embodiments, separately coating an anode active material on theanode current collector can be omitted, and as a result, an energydensity may be increased by controlling the amount of the metal particleadded to the first liquid electrolyte.

The first organic solvent of the first liquid electrolyte may include anether compound or a sulfone compound, wherein the ether compound maycomprise at least one of a glyme compound, a dioxolane compound, or afluorinated ether compound. The second liquid electrolyte may includeany of the above-listed organic solvents of the first liquidelectrolyte, and/or a carbonate compound.

For example, the glyme compound may comprise at least one of ethyleneglycol dimethylether(1,2-dimethoxyethane), ethylene glycoldiethylether(1,2-diethoxyethane), propylene glycol dimethylether,propylene glycol diethylether, butylene glycol dimethylether, butyleneglycol diethylether, diethylene glycol dimethylether, triethylene glycoldimethylether, tetraethylene glycol dimethylether, diethylene glycoldiethylether, triethylene glycol diethylether, tetraethylene glycoldiethylether, dipropylene glycol dimethylether, tripropylene glycoldimethylether, tetrapropylene glycol dimethylether, dipropylene glycoldiethylether, tripropylene glycol diethylether, tetrapropylene glycoldiethylether, dibutylene glycol dimethylether, tributylene glycoldimethylether, tetrabutylene glycol dimethylether, dibutylene glycoldiethylether, tributylene glycol diethylether, or tetrabutylene glycoldiethylether. For example, the fluorinated ether compound may be atleast one of 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether,or 2,2,3,3,4,4,5,5-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether.

The dioxolane compound may include, for example, at least one of1,3-dioxolane, 4,5-dimethyl-1,3-dioxolane, 4,5-diethyl-1,3-dioxolane,4-methyl-1,3-dioxolane, 4-ethyl-1,3-dioxolane, 2-methyl-1,3-dioxolane,2-vinyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, or2-ethyl-2-methyl-1,3-dioxolane.

The sulfone compound may include, for example, at least one of dimethylsulfone, diethyl sulfone, or ethylmethyl sulfone.

The carbonate compound may include, for example, at least one ofethylene carbonate, propylene carbonate, dimethyl carbonate, diethylcarbonate, butylene carbonate, ethylmethyl carbonate, fluoroethylenecarbonate, methylpropyl carbonate, ethylpropyl carbonate,methylisopropyl carbonate, dipropyl carbonate, or dibutyl carbonate.

The first organic solvent may be include, for example, a fluorinatedether compound.

The amount of the fluorinated ether compound may be about 50 vol. % orless, and in some embodiments, about 0.1 vol. % to about 50 vol. %, andin some other embodiments, about 1 vol. % to about 30 vol. %, or about 5vol % to about 25 vol %, based on a total amount of the first organicsolvent.

The fluorinated ether compound has a high flash point of about 80° C. orgreater and excellent flame retardancy. When such a fluorinated ethercompound is used as an organic solvent for a liquid electrolyte, ananodeless lithium metal battery having improved high-temperaturestability may be manufactured. The fluorinated ether compound has astructure in which fluorinated functional groups are bonded to a —CH₂—O—moiety, and has a small polarity. Thus, the fluorinated ether compoundmay have excellent miscibility with an ether solvent capable ofsolvating lithium ions and having high dissolution capability, such asdimethyl ether (DME).

The fluorinated ether compound represented by Formula 1 may be at leastone of HCF₂CF₂CH₂OCF₂CF₂H, HCF₂CF₂CH₂OCF₂CF₂CF₂CF₂H, HCF₂CF₂OCH₂CF₃,HCF₂CF₂OCH₂CH₂OCF₂CF₂H, HCF₂CF₂OCH₂CH₂CH₂OCF₂CF₂H,HCF₂CF₂CH₂OCF₂CF₂CF₂H, HCF₂CF₂OCH₂CH₂OCF₂CF₂CF₂H, orHCF₂CF₂OCH₂CH₂CH₂OCF₂CF₂CF₂H.

The fluorinated ether compound represented by Formula 1 may be, forexample, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether, or2,2,3,3,4,4,5,5-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether.

The lithium salt may be any suitable lithium salt including those usedto prepare electrolyte in the art. For example, the lithium salt mayinclude at least one of LiSCN, LiN(CN)₂, Li(CF₃SO₂)₃C,Li(FSO₂)₂N(LiFSI), LiC₄F₉SO₃, LiN(SO₂CF₂CF₃)₂, LiPF₃(C₂F₅)₃, LiCl, LiF,LiBr, LiI, LiB(C₂O₄)₂, LiPF₆, LiPF₅(CF₃), LiPF₅(C₂F₅), LiPF₅(C₃F₇),LiPF₄(CF₃)₂, LiPF₄(CF₃)(C₂F₅), LiPF₃(CF₃)₃, LiPF₃(CF₂CF₃)₃, LiPF₄(C₂O₄),LiBF₄, LiBF₃(C₂F₅), lithium bis(oxalato) borate (LiBOB), lithiumoxalyldifluoroborate (LIODFB), lithium difluoro(oxalato)borate (LiDFOB),lithium bis(trifluoro methanesulfonyl)imide (LiTFSI, LiN(SO₂CF₃)₂),lithium bis(fluorosulfonyl)imide (LiFSI, LiN(SO₂F)₂), LiN(SO₂C₂F₅)₂,LiCF₃SO₃, LiAsF₆, LiSbF₆, or LiClO₄.

The first liquid electrolyte and the second liquid electrolyte may eachhave a viscosity at 25° C. of about 5 centipoise (cP) or less, or about3 cP or less, or about 2 cP or less. When the first liquid electrolyteand the second liquid electrolyte have a viscosity within this range,ions may freely migrate in the first liquid electrolyte or the secondliquid electrolyte, and ion conductivity may be improved. The firstliquid electrolyte and the second liquid electrolyte may each have anion conductivity at 25° C. of about 1.0 milliSiemens per centimeter(mS/cm) or greater, or about 2 mS/cm ore greater, or about 4 mS/cm orgreater, and in some embodiments, about 1 mS/cm to about 10 mS/cm, orabout 1 mS/cm to about 5 mS/cm.

In addition to the above-listed organic solvents, the first liquidelectrolyte and the second liquid electrolyte may each independentlyfurther include at least one of γ-butyrolactone, succinonitrile,adiponitrile, benzonitrile, acetonitrile, tetrahydrofuran,2-methyltetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulfoxide, dioxane, sulfolane, dichloroethane, chlorobenzene,or nitrobenzene.

The composite electrolyte may be, for example, in a gel or semi-solidform. When the composite electrolyte has a gel or semi-solid form, themetal particle may freely expand during charge and discharge, avoidinglimitations to expansion present in a solid, and avoidingexpansion-related degradation mechanisms.

In an embodiment, the composite electrolyte may be prepared by combiningmetal particle with the first liquid electrolyte to prepare a compositeelectrolyte composition, coating the composite electrolyte compositionon the anode current collector, and drying the coated compositeelectrolyte composition.

The anode current collector may be a mesh-type current collector. Whenusing a mesh-type current collector as the anode current collector, theanode current collector may be effectively impregnated with thecomposite electrolyte. Accordingly, the composite electrolyte may notinclude a non-woven fabric.

The composite electrolyte composition may be prepared by mixing themetal particle comprising at least one of lithium metal or a lithiummetal alloy with a first liquid electrolyte. The composition for formingthe composite electrolyte may have a gel or semi-solid form. Thecomposition may have a viscosity at 25° C. of about 90 cP or less, forexample, about 80 cP or less, for example, about 60 cP or less, forexample, about 50 cP or less, for example, about 30 cP or less, forexample, about 10 cP or less, for example, about 5 cP or less, or about4.5 cP or less, or about 4 cP or less, and in some embodiments, about 1cP to about 5 cP, or about 2 cP to about 4.5 cP, or about 2.5 cP toabout 4 cP, but the viscosity of the composition is not limited thereto.

Optionally, after the coating of the composite electrolyte compositionon the anode current collector, a non-woven fabric may be disposedthereon.

Next, the solid electrolyte, a cathode including a cathode activematerial layer, and a cathode current collector may be disposed on theresulting structure including the composite electrolyte composition onthe anode current collector, thereby manufacturing the anodeless lithiummetal battery according to an embodiment.

In the anodeless lithium metal battery according to an embodiment, thecomposite electrolyte may release a lithium ion during discharge, andthe lithium ion may migrate to the at least one of lithium metal or alithium metal alloy in the composite electrolyte during charge, and thenbe electrodeposited on a surface of the at least one of lithium metaland a lithium metal alloy.

In the lithium metal battery according to one or more embodiments, thelithium from the metal particle including at least one of metal or alithium metal alloy may be deposited on the anode current collectorduring charge. The deposited lithium may have an interconnected networkstructure that is formed upon charge of the anodeless lithium metalbattery. Conventional lithium anode thin film do not have a free volumebefore and after charging, and are expanded upward and downward,resulting in more stress due to dendrite formation. Unlike the lithiumanode thin film that may only expand in an upper or lower direction, themetal particle in the anodeless lithium metal battery may expand in aradial direction as shown in FIG. 1C, leading to nearly zero stress,thus improving energy density and reducing an expansion rate of thebattery after charging and discharging.

In the anodeless lithium metal battery according to one or moreembodiments, the interconnected structure of the lithium metal and/orthe lithium alloy may be in the form of a particle or in the form of alayer on a surface of the anode current collector. The interconnectedstructure of the deposited lithium metal may be in the form of acontinuous or discontinuous layer. When the interconnected structure ofthe lithium metal and/or the lithium alloy forms a layer on the anodecurrent collector, a thickness of the layer may be about 10% or less,and in some embodiments, about 5% or less, and in some otherembodiments, about 2% or less, and in still other embodiments, about 1or less, and in yet other embodiments, about 0.1 to about 10%, or about0.1 to about 5%, or about 0.1% to about 1%, with respect to a thicknessof the cathode.

In the anodeless lithium metal battery according to one or moreembodiments, a continuous or discontinuous lithium metal layer may notbe formed on the anode current collector after charging and dischargingof the anodeless lithium metal battery.

After charge and discharge, the composite electrolyte may contact thenegative electrode current collector. Here, a lithium metal layer may benot formed uniformly or not at all between the negative electrodecurrent collector and the composite electrolyte even after charge anddischarge.

A contact area between at least one of the lithium metal and the lithiumalloy and the first liquid electrolyte of the composite electrolyte maybe at least twice the contact area between at least one of lithium metallayer and lithium alloy layer of the same volume and the firstelectrolyte.

The cathode according to an embodiment may be manufactured in thefollowing manner. For example, a cathode active material, a conductingagent, a binder, and a solvent may be mixed together to prepare acathode active material layer composition. The cathode active materiallayer composition may be directly coated on a metallic current collectorto prepare a cathode. In some other embodiments, the cathode activematerial layer composition may be cast on a separate support to form acathode active material film. The cathode active material film may thenbe separated from the support and laminated on a metallic currentcollector, to thereby prepare a cathode. Any suitable cathode may beused, the cathode may be any of a variety of types, and not limited tothese examples.

In an embodiment, the cathode active material may be a lithium compositeoxide. Any suitable lithium composite oxide may be used. For example,the lithium composite oxide may be a composite oxide of lithium with atleast one of a metal of cobalt, manganese, or nickel. In an embodiment,the cathode active material may be a compound represented by:Li_(a)A_(1−b)B′_(b)D₂ (wherein 0.90≤a≤1.8, and 0≤b≤0.5);Li_(a)E_(1−b)B′_(b)O_(2−c)D_(c) (wherein 0.90≤a≤1.8, 0≤b≤0.5, and0≤c≤0.05); LiE_(2−b)B′_(b)O_(4−c)D_(c) (wherein 0≤b≤0.5, and 0≤c≤0.05);Li_(a)Ni_(1−b−c)CO_(b)B′_(c)D_(α) (wherein 0.90≤a≤1.8, 0≤b≤0.5,0≤c≤0.05, and 0<α≤2); Li_(a)Ni_(1−b−c)CO_(b)B′_(c)O_(2−α)F′_(α) (wherein0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0<α≤2);Li_(a)Ni_(1−b−c)CO_(b)B′_(c)O_(2−α)F′2 (wherein 0.90≤a≤1.8, 0≤b≤0.5,0≤c≤0.05, and 0<α≤2); Li_(a)Ni_(1−b−c)Mn_(b)B′_(c)D_(α) (wherein0.90≤α≤1.8, 0≤b≤0.5, 0≤c≤0.05, and 0<α≤2);Li_(a)Ni_(1−b−c)Mn_(b)B′_(c)O_(2−α)F′_(α) (wherein 0.90≤α≤1.8, 0≤b 0.5,0≤c≤0.05, and 0<α≤2); Li_(a)Ni_(1−b−c)Mn_(b)B′_(c)O_(2−α)F′₂ (wherein0.90≤a≤1.8, 0 b≤0.5, 0≤c≤0.05, and 0<α≤2); Li_(a)Ni_(b)E_(c)G_(d)O₂(wherein 0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, and 0.001≤d≤0.1);Li_(a)Ni_(b)Co_(c)Mn_(d)GeO₂ (wherein 0.90≤a≤1.8, 0≤b≤0.9, 0≤c 0.5,0≤d≤0.5, and 0.001≤e≤0.1); Li_(a)NiG_(b)O₂ (wherein 0.90≤a≤1.8, and0.001≤b≤0.1); Li_(a)CoG_(b)O₂ (wherein 0.90≤a≤1.8, and 0.001≤b≤0.1);Li_(a)MnG_(b)O₂ (wherein 0.90≤a≤1.8, and 0.001≤b≤0.1); Li_(a)Mn₂G_(b)O₄(wherein 0.90≤a≤1.8, and 0.001≤b≤0.1); QO₂; QS₂; LiQS₂; V₂O₅; LiV₂O₅;LiI′O₂; LiNiVO₄; Li_((3−f))J₂(PO₄)₃ (wherein 0≤f≤2); Li_((3−f))Fe₂(PO₄)₃(wherein 0≤f≤2); LiFePO₄, or a combination thereof.

In the above formulae, A may be nickel (Ni), cobalt (Co), manganese(Mn), or a combination thereof; B′ may be aluminum (Al), nickel (Ni),cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg),strontium (Sr), vanadium (V), a rare earth element, or a combinationthereof; D may be oxygen (O), fluorine (F), sulfur (S), phosphorus (P),or a combination thereof; F′ may be fluorine (F), sulfur (S), phosphorus(P), or a combination thereof; G may be aluminum (Al), chromium (Cr),manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce),strontium (Sr), vanadium (V), or a combination thereof; Q may betitanium (Ti), molybdenum (Mo), manganese (Mn), or a combinationthereof; I′ may be chromium (Cr), vanadium (V), iron (Fe), scandium(Sc), yttrium (Y), or a combination thereof; and J may be vanadium (V),chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), ora combination thereof.

The compounds listed above as the cathode active material may have asurface coating layer (hereinafter, also referred to as “coatinglayer”). Alternatively, a combination of a compound without a coatinglayer and a compound having a coating layer may be used. In anembodiment, the coating layer may include at least one compound of acoating element including an oxide, a hydroxide, an oxyhydroxide, anoxycarbonate, or a hydroxycarbonate of the coating element. In anembodiment, the compounds for forming the coating layer may be amorphousor crystalline. In an embodiment, the coating element for forming thecoating layer may be at least one of magnesium (Mg), aluminum (Al),cobalt (Co), potassium (K), sodium (Na), calcium (Ca), silicon (Si),titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga),boron (B), arsenic (As), or zirconium (Zr). In an embodiment, thecoating layer may be formed using any method that does not adverselyaffect the physical characteristics of the cathode active material whena compound of the coating element is used. For example, the coatinglayer may be formed using spray coating or dipping. Details of suchcoating methods can be determined by one of skill in the art withoutundue experimentation, and thus further detailed description thereofwill be omitted.

Non-limiting examples of the conducting agent may include: carbon black;graphite particle; natural graphite; artificial graphite; acetyleneblack; Ketjen black; carbon fiber; carbon nanotube; metal powder, metalfiber or metal tube of copper, nickel, aluminum, and silver; and aconductive polymer such as polyphenylene derivative. However,embodiments are not limited thereto, and any conducting agent suitablefor a lithium metal battery may be used. A combination comprising atleast one of the foregoing may be used.

Non-limiting examples of the binder may include vinylidenefluoride/hexafluoropropylene copolymers, polyvinylidene fluoride,polyimide, polyethylene, polyester, polyacrylonitrile, polymethylmethacrylate, polytetrafluoroethylene (PTFE), a carboxymethylcellulose/styrene-butadiene rubber (SMC/SBR) copolymer, a styrenebutadiene rubber-based polymer, or a combination thereof. However,embodiments are not limited thereto, and any material suitable for useas a binder in a lithium metal battery may be used.

For example, the solvent may be N-methyl-pyrrolidone, acetone, or water.However, examples of the solvent are not limited thereto. Any suitablematerial available as a solvent in the art may be used.

The amounts of the cathode active material, the conducting agent, thebinder, and the solvent may be determined by those of skill in the artwithout undue experimentation. At least one of the conducting agent, thebinder, and the solvent may be omitted depending on the use and thestructure of a lithium metal battery.

The anodeless lithium metal battery according to one or more embodimentsmay further include a separator.

For example, the separator may be a single-layer structure or amulti-layer structure, including at least one or two layers ofpolyethylene, polypropylene, polyvinylidene fluoride, or a combinationthereof. For example, the separator may be a mixed multilayer structure,such as a two-layer separator of polyethylene/polypropylene, athree-layer separator of polyethylene/polypropylene/polyethylene, or athree-layer separator of polypropylene/polyethylene/polypropylene.

A battery case may have a cylindrical, rectangular, pouch, or thin filmshape. For example, the anodeless lithium metal battery according to oneor more embodiments may be a lithium ion battery. For example, theanodeless lithium metal battery according to one or more embodiments maybe a lithium air battery, a lithium sulfur battery, or the like.

The lithium metal battery according to any of the above-describedembodiments may have improved lifetime characteristics and highdischarge rate characteristics, and thus may be used in, for example,electric vehicles (EVs). For example, the lithium metal battery may beused in hybrid vehicles such as plug-in hybrid electric vehicles (PHEV)or the like. The lithium metal battery may also be used in the fieldswhere storage of a large amount of power is required. For example, thelithium metal battery may be used in electric bikes, power tools, andthe like.

In some embodiments, when a plurality of lithium metal batteriesaccording to one or more embodiments are stacked upon one another, a geltype electrolyte may be arranged between the cathode and theliquid-impermeable ion-conductive composite membrane in each battery.For example, the gel type electrolyte may include a vinylidenedifluoride-hexafluoropropylene (VDF-HFP) copolymer, a lithium salt, andan organic solvent.

One or more embodiments of the present disclosure will now be describedin detail with reference to the following examples. However, theseexamples are only for illustrative purposes and are not intended tolimit the scope of the one or more embodiments of the presentdisclosure.

EXAMPLES Example 1: Anodeless Lithium Metal Battery

After a composition for forming a composite electrolyte was applied ontoa copper foil used as an anode current collector, a cellulose non-wovenfabric (having a porosity of about 50% and a thickness of about 30 μm)was disposed thereon, and the resulting structure was dried to form thecomposite electrolyte (having a thickness of about 50 μm) on the copperfoil.

The composite electrolyte composition was prepared by mixing 3.5 molar(M) of a first liquid electrolyte with lithium metal powder (having asize of about 50 μm), and the first liquid electrolyte was obtained bymixing lithium bis(fluorosulfonyl)imide (LiFSI) with ethylene glycoldimethylether(1,2-dimethoxyethane:DME). The amount of the lithium metalpowder was about 20 parts by weight with respect to 100 parts by weightof a total weight of the composite electrolyte (i.e., a total weight ofthe lithium salt, the organic solvent, and the lithium metal powder).

A cathode was manufactured as follows.

A liquid electrolyte for the cathode was prepared by mixing 0.4 M oflithium bis(trifluoro methanesulfonyl)imide (LiTFSI), 0.6 M of lithiumbis(oxalate)borate (LiBOB), and ethylene carbonate with ethylmethylcarbonate in a volume ratio of about 3:7.

A cathode active material layer composition was obtained by mixingLiNi_(1/3)Co_(1/3)Mn_(1/3)O₂, a carbon black conducting agent (Super-P™,Timcal Ltd.), polyvinylidene fluoride (PVdF), and N-methyl pyrrolidone.A weight ratio of LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂ to the conducting agent,and to the PVdF in the cathode active material layer composition wasabout 97:1.5:1.5. The cathode active material layer composition wascoated on an aluminum foil (having a thickness of about 15 μm) and thendried at about 25° C. Then, the resulting dried product was furtherdried under vacuum at about 110° C., thereby manufacturing the cathode.

A solid electrolyte having a thickness of about 90 μm was arrangedbetween the cathode and the composite electrolyte on the anode currentcollector and assembled together, thereby manufacturing an anodelesslithium metal battery.

A Li_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂ (LTAP) membrane having a thickness ofabout 90 μm was used as the solid electrolyte. The cathode was arrangedon a surface of the solid electrolyte, while the composite electrolyteand the anode current collector were sequentially arranged on the othersurface of the solid electrolyte opposite to the cathode. Then, thecathode, the solid electrolyte, the composite electrolyte, and the anodecurrent collector were assembled together, thereby manufacturing theanodeless lithium metal battery.

Example 2: Anodeless Lithium Metal Battery

An anodeless lithium metal battery was manufactured in the same manneras in Example 1, except that a composite membrane containing LTAP andpolyvinyl alcohol was used as the solid electrolyte, instead of the LTAPmembrane. In the composite membrane containing LTAP and polyvinylalcohol, the amount of the polyvinyl alcohol was about 68 parts byweight with respect to 100 parts by weight of the composite membrane.The composite membrane had a thickness of about 70 μm and was preparedaccording to Example 1 of US-2015-0079485-A1, the content of which isincorporated herein by reference in its entirety.

Example 3: Anodeless Lithium Metal Battery

An anodeless lithium metal battery was manufactured in the same manneras in Example 1, except that lithium metal powder having a size of about20 μm was used to prepare the composite electrolyte.

Examples 4 and 5: Anodeless Lithium Metal Battery

Anodeless lithium metal batteries were manufactured in the same manneras in Example 1, except that the amount of the lithium metal powder waschanged to about 1 part by weight and about 50 parts by weight,respectively, with respect to 100 parts by weight of the compositeelectrolyte.

Examples 6 and 7: Anodeless Lithium Metal Battery

Anodeless lithium metal batteries were manufactured in the same manneras in Example 1, except that 2 M of the first liquid electrolyte and 4 Mof the first liquid electrolyte were used, respectively, instead of 3.5M of the first liquid electrolyte.

Examples 8 and 9: Anodeless Lithium Metal Battery

Anodeless lithium metal batteries were manufactured in the same manneras in Example 1, except that the thickness of the LTAP membrane waschanged to about 20 μm and about 45 μm, respectively.

Example 10: Anodeless Lithium Metal Battery

An anodeless lithium metal battery was manufactured in the same manneras in Example 1, except that the composition for forming the compositeelectrolyte was supplied onto a copper mesh used as the anode currentcollector, and a cellulose non-woven fabric was not disposed thereon.

Due to the use of the copper mesh used as the anode current collector inExample 10, which may be impregnated with the composition for formingthe composite electrolyte, the cellulose non-woven fabric used inExample 1 was not necessary.

Examples 11 and 12: Anodeless Lithium Metal Battery

Anodeless lithium metal batteries were manufactured in the same manneras in Example 1, except that the thickness of the composite electrolytewas changed to about 10 μm and to about 150 μm, respectively.

Comparative Example 1: Anodeless Lithium Metal Battery

A copper foil as an anode current collector was dipped in a 1 M HClsolution for about 10 minutes, washed with distilled water and acetone,and then dried.

A cathode was manufactured in the following manner by coating a thinfilm of a cathode active material layer composition on an aluminum foil.A liquid electrolyte for the cathode was prepared by mixing 0.4 MLiTFSI, 0.6 M of lithium bis(oxalato)borate (LiBOB), and ethylenecarbonate and ethylmethyl carbonate in a volume ratio of about 3:7. Theliquid electrolyte was disposed between the cathode and a solidelectrolyte described below.

The cathode active material layer composition was prepared by mixingLiNi_(1/3)Co_(1/3)Mn_(1/3)O₂, a conducting agent (Super-P, availablefrom Timcal Ltd.), polyvinylidene fluoride (PVdF), and N-methylpyrrolidone to obtain the cathode active material layer composition. Aweight ratio of LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂ to the conducting agent tothe PVdF in the cathode active material layer composition was about97:1.5:1.5.

The cathode active material layer composition was coated on the aluminumfoil (having a thickness of about 15 μm) and dried at about 25° C., thenfurther under vacuum at about 100° C. or less, thereby manufacturing thecathode.

The cathode, the liquid electrolyte on the anode current collector,which was prepared above as the anode electrolyte by mixing 3.5 M oflithium bis(fluorosulfonyl)imide (LiFSI) with dimethylether (DME), andthe separator (Celgard 2045) were used in manufacturing an anodelesslithium metal battery.

A Li_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂ (LTAP) membrane having a thickness ofabout 90 μm was used as a solid electrolyte. The cathode was disposed ona surface of the solid electrolyte, while the liquid electrolyte used asthe anode electrolyte and the anode current collector were sequentiallydisposed on the other surface of the solid electrolyte opposite to thecathode. Then, the cathode, the solid electrolyte, the compositeelectrolyte, and the anode current collector were assembled together,thereby manufacturing the anodeless lithium metal battery.

The liquid electrolyte used as the anode electrolyte in ComparativeExample 1 did not contain lithium metal powder, unlike the compositeelectrolyte of Example 1. In the anodeless lithium metal battery ofComparative Example 1, the liquid electrolyte was prone to reduction dueto a potential generated between the lithium and current collector metalduring deposition of lithium, and formation of lithium dendrite wasfacilitated, thus reducing change-discharge efficiency and lifetime ofthe lithium metal battery.

Comparative Example 2: Lithium Metal Battery

A polyethylene/polypropylene separator (G1212A, available from Asahi)was disposed between a lithium metal anode (having a thickness of about20 μm) and a cathode, and a 3.5 M of a liquid electrolyte obtained bymixing LiTFSI with dimethylether (DME) as an organic solvent was used.

The cathode was manufactured using a cathode active material layercomposition obtained by mixing LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂, aconducting agent (Super-P, available from Timcal Ltd.), polyvinylidenefluoride (PVdF), and N-methyl pyrrolidone. A mixed weight ratio ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O₂ to the conducting agent to PVdF in thecathode composition was about 97:1.5:1.5. The cathode composition wascoated on an aluminum foil (having a thickness of about 15 μm) and thendried at about 25° C. Then, the resulting dried product was furtherdried under vacuum at about 110° C., thereby manufacturing the cathode.

Evaluation Example 1: Impedance Analysis

1) Initial Impedance

Initial impedance characteristics of the lithium metal batteries ofExample 1 and Comparative Example 1 were evaluated by measuringresistance using a 2-probe method with an impedance analyzer (Solartron1260A Impedance/Gain-Phase Analyzer) at about 25° C. in a frequencyrange of about 10⁶ to 0.1 megahertz (MHz) at a voltage bias of about 10millivolts (mV).

Nyquist plots obtained from the results of the impedance measurementsthat were performed at 24 hours from the manufacture of the anodelesslithium metal batteries of Example 1 and Comparative Example 1 are shownin FIG. 6A. In FIG. 6A, a bulk resistance of an electrode depends fromthe position and size of a semicircle, and may be represented as adifference between the left x-intercept and the right x-intercept of thesemicircle.

Referring to FIG. 6A, the anodeless lithium metal battery of Example 1was found to have a remarkably reduced bulk resistance, compared to theanodeless lithium metal battery of Comparative Example 1.

2) Impedance after One Cycle

Impedance characteristics after one cycle of the lithium metal batteriesof Example 1 and Comparative Example 1 were evaluated in the followingmanner.

Each of the lithium metal batteries was charged at about 25° C. with aconstant current of 0.1 C to a voltage of about 4.30 Volts (V) (withrespect to Li), and then with a constant voltage of 4.30 V until acutoff current of 0.05 C was reached, and was then discharged with aconstant current of 0.1 C to a voltage of about 2.8 V (with respect toLi) (Formation process, 1^(st) cycle). This charging and dischargingprocess was performed an additional two times to complete the formationprocess. A C rate is a discharge rate of a cell, and is obtained bydividing a total capacity of the cell by a total discharge period oftime of 1 hour, e.g., a C rate for a battery having a discharge capacityof 1.6 ampere-hours would be 1.6 amperes.

Subsequently, each of the lithium metal batteries was charged at about25° C. with a constant current of 0.1 C (0.38 milliampere hours persquare centimeter (mA/cm²)) to a voltage of about 4.40 V (with respectto Li), and then with a constant voltage of 4.40 V until a cutoffcurrent of 0.05 C was reached. After this charging once, impedancecharacteristics after a single cycle of each of the lithium metalbatteries were evaluated by measuring resistance using a 2-probe methodwith an impedance analyzer (Solartron 1260A Impedance/Gain-PhaseAnalyzer) in a frequency range of about 10⁶ to 0.1 MHz, at a voltagebias of about 10 mV at about 25° C. The evaluation results are shown inFIG. 6B.

Referring to FIG. 6B, the resistance of the anodeless lithium metalbattery of Comparative Example 1 was reduced compared to that beforecharging and discharging after one cycle of charging and discharging,but still increased as compared with the anodeless lithium metal batteryof Example 1

Evaluation Example 2: Charge-Discharge Characteristics

The lithium metal batteries of Example 1 and Comparative Examples 1 and2 were charged at about 25° C. with a constant current of 0.1 C to avoltage of about 4.30 V (with respect to Li), and then with a constantvoltage of 4.30 V until a cutoff current of 0.05 C was reached, and werethen discharged with a constant current of 0.1 C to a voltage of about2.8 V (with respect to Li) (Formation process, 1st cycle). This chargingand discharging process was performed further twice to complete theformation process.

After the formation process, each of the lithium metal batteries wascharged at room temperature (25° C.) with a constant current of i) 0.5 Cor ii) 1 C in a voltage range of about 3.0 V to 4.4 V (with respect toLi) and then discharged with a constant current of 0.2 C (0.72 mA) untila cutoff voltage of 3.0. V was reached. This charging and dischargingcycle was repeated 50 times in total. A Coulombic efficiency wascalculated using Equation 1.Coulombic efficiency (%)=(Discharge capacity of each cycle/Chargecapacity of each cycle)×100%  Equation 1

The evaluation results of the charge-discharge characteristics are shownin FIGS. 2A, 2B, 3A, 3B, 4A, and 4B. FIGS. 2A and 2B show changes incapacity and Coulombic efficiency, respectively, with respect to thenumber of cycles in the anodeless lithium metal battery of Example 1.FIGS. 3A and 3B show changes in capacity and Coulombic efficiency,respectively, with respect to the number of cycles in the anodelesslithium metal battery of Comparative Example 1. FIGS. 4A and 4B showchanges in capacity and Coulombic efficiency, respectively, with respectto the number of cycles in the lithium metal battery of ComparativeExample 2.

Referring to FIGS. 3A and 3B, the anodeless lithium metal battery ofComparative Example 1 was found to have a charge and dischargeefficiency (Coulombic efficiency) of less than 90% and a reducedcapacity retention of less than 50% in 10 cycles.

Referring to FIGS. 4A and 4B, the lithium metal battery of ComparativeExample 2 was found to maintain a Coulombic efficiency (charge anddischarge efficiency) of about 99.8% and a capacity retention of about93% after 50 cycles at 0.5 C. Referring to FIGS. 2A and 2B, theanodeless lithium metal battery of Example 1 was found to maintain agood charge and discharge efficiency and to have no reduction incapacity retention in 50 cycles at 0.5 C.

Charge and discharge characteristics of the anodeless lithium metalbatteries of Examples 2 to 12 were evaluated using the same method asapplied to the anodeless lithium metal battery of Example 1.

As a result of the evaluation, the anodeless lithium metal batteries ofExamples 2 to 12 were found to have equivalent or similar charge anddischarge characteristics to those of the anodeless lithium metalbattery of Example 1.

Evaluation Example 3: Rate Capability

Rate capabilities of the lithium metal batteries of Example 1 andComparative Example 2 were evaluated using the following method.

Each of the lithium metal batteries of Example 1 and Comparative Example2 was charged with a constant current (0.2 C) and a constant voltage(4.3V, 0.05 C cut-off). After a rest for about 10 minutes, the lithiummetal batteries were discharged with a constant current (0.1 C, 0.5 C,or 1 C) until a voltage of about 3.0V was reached. In particular, withperiodic changing of the discharge rate to 0.1 C, 0.5 C, or 1 C at everyincrease in charge and discharge cycle number, high-rate dischargecharacteristics (referred to also as “rate capability”) of each lithiummetal battery was evaluated. During 1^(st) to 3^(rd) charge anddischarge cycles, each coin cell was discharged at a rate of 0.1 C. Arate capability of each coin half cell was defined by Equation 2.Rate capability [%]=(Discharge capacity when discharged at a specificconstant current)/(Discharge capacity when discharged at a dischargerate of 0.1 C)×100%  Equation 2

The evaluation results are shown in FIG. 5.

Referring to FIG. 5, the anodeless lithium metal battery of Example 1was found to have similar capacity characteristics at 0.5 C to those ofthe lithium metal battery of Comparative Example 2. However, theanodeless lithium metal battery of Example 1 had remarkably improvedcapacity characteristics at 1.0 C or greater, compared to those of thelithium metal battery of Comparative Example 2.

As described above, according to the embodiment, an anodeless lithiummetal battery having improved energy density and lifetimecharacteristics may be manufactured.

It should be understood that embodiments described herein should beconsidered in a descriptive sense only and not for purposes oflimitation. Descriptions of features, advantages, or aspects within eachembodiment should be considered as available for other similar featuresor aspects in other embodiments.

While one or more embodiments have been described with reference to thefigures, it will be understood by those of ordinary skill in the artthat various changes in form and details may be made therein withoutdeparting from the spirit and scope as defined by the following claims.

What is claimed is:
 1. An anodeless lithium metal battery comprising: acathode comprising a cathode current collector and a cathode activematerial layer comprising a cathode active material on the cathodecurrent collector; an anode current collector; and a compositeelectrolyte between the cathode and the anode current collector, whereinthe composite electrolyte comprises a first electrolyte comprising alithium salt and an organic solvent, wherein the organic solventcomprises at least one of an ether compound or a sulfone compound, and ametal comprising at least one of lithium metal or a lithium metal alloy,wherein the metal is in a form of a particle.
 2. The anodeless lithiummetal battery of claim 1, wherein the particle has a particle size ofabout 5 micrometers to about 50 micrometers.
 3. The anodeless lithiummetal battery of claim 1, wherein the lithium metal alloy compriseslithium and at least one of Si, Sn, Al, Ge, Pb, Bi, Sb, Mg, In, Ca, Ti,V, a Si—Y′ alloy, wherein Y′ is at least one of an alkaline metal, analkaline earth metal, a Group 13 to Group 16 element, a transitionmetal, or a rare earth element and is not Si, a Sn—Y′ alloy, wherein Y′is at least one of an alkaline metal, an alkaline earth metal, a Group13 to Group 16 element, a transition metal, or a rare earth element andis not Sn, or MnO_(x), wherein 0<x≤2.
 4. The anodeless lithium metalbattery of claim 1, wherein an amount of the metal is about 1 part byweight to about 50 parts by weight, with respect to 100 parts by weightof a total weight of the composite electrolyte.
 5. The anodeless lithiummetal battery of claim 1, wherein the metal particle is lithium metal.6. The anodeless lithium metal battery of claim 1, wherein the ether isat least one of a glyme compound, a dioxolane compound, or a fluorinatedether compound.
 7. The anodeless lithium metal battery of claim 6,wherein the glyme compound is at least one of ethylene glycoldimethylether, ethylene glycol diethylether, propylene glycoldimethylether, propylene glycol diethylether, butylene glycoldimethylether, butylene glycol diethylether, diethylene glycoldimethylether, triethylene glycol dimethylether, tetraethylene glycoldimethylether, diethylene glycol diethylether, triethylene glycoldiethylether, tetraethylene glycol diethylether, dipropylene glycoldimethylether, tripropylene glycol dimethylether, tetrapropylene glycoldimethylether, dipropylene glycol diethylether, tripropylene glycoldiethylether, tetrapropylene glycol diethylether, dibutylene glycoldimethylether, tributylene glycol dimethylether, tetrabutylene glycoldimethylether, dibutylene glycol diethylether, tributylene glycoldiethylether, or tetrabutylene glycol diethylether, the fluorinatedether compound is at least one of 1,1,2,2-tetrafluoroethyl2,2,3,3-tetrafluoropropyl ether, or 2,2,3,3,4,4,5,5-octafluoropentyl1,1,2,2-tetrafluoroethyl ether, the dioxolane compound is at least oneof 1,3-dioxolane, 4,5-dimethyl-1,3-dioxolane, 4,5-diethyl-1,3-dioxolane,4-methyl-1,3-dioxolane, 4-ethyl-1,3-dioxolane, 2-methyl-1,3-dioxolane,2-vinyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, or2-ethyl-2-methyl-1,3-dioxolane, and the sulfone compound is at least oneof dimethyl sulfone, diethyl sulfone, or ethylmethyl sulfone.
 8. Theanodeless lithium metal battery of claim 6, wherein the organic solventcomprises a fluorinated ether compound, and wherein an amount of thefluorinated ether compound is about 0.1 volume percent to about 50volume percent, based on a total volume of the organic solvent.
 9. Theanodeless lithium metal battery of claim 1, wherein the compositeelectrolyte further comprises a non-woven fabric, and wherein the metalparticle is supported on the non-woven fabric.
 10. The anodeless lithiummetal battery of claim 9, wherein the non-woven fabric comprises atleast one of cellulose, polyester, polyetherimide, polyethylene,polypropylene, polyethylene terephthalate, polybutylene terephthalate,polyamide, polyacetal, polycarbonate, polyimide, polyether ketone,polyether sulfone, polyphenylene oxide, polyphenylene sulfide,polyethylene naphthalate, polytetrafluoroethylene, polyvinylidenefluoride, polyvinyl chloride, polyacrylonitrile, nylon, orpolypara-phenylene benzobisoxazole.
 11. The anodeless lithium metalbattery of claim 1, wherein a concentration of the lithium salt in thefirst electrolyte is about 1 molar to about 8 molar.
 12. The anodelesslithium metal battery of claim 11, wherein the concentration of thelithium salt in the first electrolyte is about 2 molar to about 5 molar.13. The anodeless lithium metal battery of claim 11, wherein the lithiumsalt comprises at least one of LiSCN, LiN(CN)₂, Li(CF₃SO₂)₃C,Li(FSO₂)₂N(LiFSI), LiC₄F₉SO₃, LiN(SO₂CF₂CF₃)₂, LiPF₃(C₂F₅)₃, LiCl, LiF,LiBr, LiI, LiB(C₂O₄)₂, LiPF₆, LiPF₅(CF₃), LiPF₅(C₂F₅), LiPF₅(C₃F₇),LiPF₄(CF₃)₂, LiPF₄(CF₃)(C₂F₅), LiPF₃(CF₃)₃, LiPF₃(CF₂CF₃)₃,LiPF₄(C₂O₄)₂, LiBF₄, LiBF₃(C₂F₅), lithium bis(oxalato)borate, lithiumoxalyldifluoroborate, lithium difluoro(oxalato)borate, lithiumbis(trifluoro methanesulfonyl)imide, LiN(SO₂CF₃)₂, lithiumbis(fluorosulfonyl)imide, LiN(SO₂F)₂, LiN(SO₂C₂F₅)₂, LiCF₃SO₃, LiAsF₆,LiSbF₆, or LiClO₄.
 14. The anodeless lithium metal battery of claim 1,wherein the composite electrolyte is in a form of a semi-solid.
 15. Theanodeless lithium metal battery of claim 1, wherein the anode currentcollector is a mesh current collector.
 16. The anodeless lithium metalbattery of claim 1, wherein the metal is in a form of an interconnectedstructure comprising interconnected particles of the metal and on asurface of the anode current collector after charging and dischargingthe anodeless lithium metal battery.
 17. The anodeless lithium metalbattery of claim 1, further comprising a solid electrolyte layer betweenthe composite electrolyte and the cathode.
 18. The anodeless lithiummetal battery of claim 17, wherein the solid electrolyte has a thicknessof about 10 micrometers to about 150 micrometers.
 19. The anodelesslithium metal battery of claim 17, further comprising a porous polymermembrane between the solid electrolyte and the composite electrolyte,wherein the porous polymer membrane comprises a polyethylene membrane, apolypropylene membrane, a polyethylene terephthalate membrane, apolybutylene terephthalate membrane, a polyester membrane, a polyacetalmembrane, a polyamide membrane, a polycarbonate membrane, a polyimidemembrane, a polyether ketone membrane, a polyether sulfone membrane, apolyphenylene oxide membrane, a polyphenylene sulfide membrane, apolyethylene naphthalate membrane, or a combination thereof.
 20. Theanodeless lithium metal battery of claim 17, wherein during charging andafter a charging and discharging cycle of the anodeless lithium metalbattery, deposition of additional lithium occurs on the metal particlecomprising at least one of lithium metal or a lithium metal alloy. 21.The anodeless lithium metal battery of claim 17, wherein the solidelectrolyte is an inorganic solid electrolyte, an organic solidelectrolyte, or an organic/inorganic composite electrolyte.
 22. Theanodeless lithium metal battery of claim 21, wherein the organic solidelectrolyte comprises at least one of a polyethylene derivative, apolyethylene oxide derivative, a polypropylene oxide derivative, aphosphoric acid ester polymer, polyester sulfide, polyvinyl alcohol, orpolyvinylidene fluoride; the inorganic solid electrolyte comprises atleast one of a glassy active metal ionic conductor, an amorphous activemetal ionic conductor, a ceramic active metal ionic conductor, or aglass-ceramic active metal ionic conductor; and the organic/inorganiccomposite electrolyte comprises at least one of the organic solidelectrolyte and the inorganic solid electrolyte.
 23. The anodelesslithium metal battery of claim 17, wherein the solid electrolyte is atleast one of Li_(1+x)Ti_(2−x)Al(PO₄)₃, wherein 0≤x≤4, a materialcomprising Li, Ge, P, and S, Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3-y)O₁₂wherein 0<x<2 and 0≤y<3, BaTiO₃, Pb(Zr_(1−x)Ti_(x))O₃ wherein 0≤x<1,Pb_(1−x)La_(x)Zr_(1−y)Ti_(y)O₃, wherein 0≤x<1 and 0≤y<1,Pb(Mg_(1/3)Nb_(2/3))O₃—PbTiO₃, HfO₂, SrTiO₃, SnO₂, CeO₂, Na₂O, MgO, NiO,CaO, BaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, TiO₂, SiO₂, SiC, Li₃PO₄,Li_(x)Ti_(y)(PO₄)₃ wherein 0<x<2 and 0<y<3, Li_(x)Al_(y)Ti_(z)(PO₄)₃wherein 0<x<2, 0<y<1, and 0<z<3,Li_(1+x+y)(Al_(1−a)Ga_(a))_(x)(Ti_(1−b)Ge_(b))_(2−x)Si_(y)P_(3−y)O₁₂wherein 0≤x≤1, 0≤y≤1, 0≤a≤1, and 0≤b≤1, Li_(x)La_(y)TiO₃ wherein 0<x<2and 0<y<3, Li_(x)Ge_(y)P_(z)S_(w) wherein 0<x<4, 0<y<1, 0<z<1, and0<w<5, Li_(x)N_(y) wherein 0<x<4 and 0<y<2, Li_(x)Si_(y)S_(z) wherein0<x<3, 0<y<2, and 0<z<4, Li_(x)P_(y)S_(z) wherein 0<x<3, 0<y<3, and0<z<7, Li₂O, LiF, LiOH, Li₂CO₃, LiAlO₂, Li_(x)Al_(y)Ti_(z)(PO₄)₃,wherein 0<x<2, 0<y<1, and 0<z<3, a Li₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂ceramic, Li_(3+x)La₃M₂O₁₂ wherein 0≤x≤5 and M is Te, Nb, or Zr.
 24. Theanodeless lithium metal battery of claim 23, wherein the solidelectrolyte is Li_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂,Li_(1.3)Ti_(1.7)Al_(0.3)P₃O₁₂, Li₁₀GeP₂S₁₂, Li₇La₃Zr₂O₁₂, lithiumphosphorous oxynitride, Li₅La₃Ta₂O₁₂, Li_(0.33)La_(0.55)TiO₃,Li_(1.5)Al_(0.5)Ge_(1.5)P₃O₁₂, Li₃BO₃, Li₄SiO₄—Li₃PO₄, Li₄SiO₄,Li_(1/3)La_(1/3)TiO₃, or Li₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂.
 25. A method ofmanufacturing the anodeless lithium metal battery of claim 1, the methodcomprising: combining a metal comprising at least one of lithium metalor a lithium metal alloy with the first electrolyte to prepare acomposite electrolyte composition; coating the composite electrolytecomposition on the anode current collector; drying the coated compositeelectrolyte composition to prepare the composite electrolyte; anddisposing the anode current collector and the composite electrolyte onthe cathode comprising the cathode active material layer on a cathodecurrent collector to manufacture the anodeless lithium metal battery.26. The method of claim 25, further comprising disposing a non-wovenfabric supporting the metal particle on the non-woven fabric after thecoating of the composite electrolyte composition on the anode currentcollector.
 27. The method of claim 25, further comprising disposing aporous polymer membrane layer between the composite electrolyte and thecathode.